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WO2018028392A1 - Solution électrolytique et batterie rechargeable - Google Patents

Solution électrolytique et batterie rechargeable Download PDF

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Publication number
WO2018028392A1
WO2018028392A1 PCT/CN2017/093376 CN2017093376W WO2018028392A1 WO 2018028392 A1 WO2018028392 A1 WO 2018028392A1 CN 2017093376 W CN2017093376 W CN 2017093376W WO 2018028392 A1 WO2018028392 A1 WO 2018028392A1
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group
carbon atoms
secondary battery
electrolyte
total mass
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PCT/CN2017/093376
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English (en)
Chinese (zh)
Inventor
谢岚
史松君
王珂
王耀辉
雷腾
肖松松
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Contemporary Amperex Technology Co Ltd
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to the field of battery technologies, and in particular, to an electrolyte and a secondary battery.
  • the negative electrode of a commercial lithium ion secondary battery mainly uses a graphite active material, and its lithium insertion potential is about 0.1 V (vs. Li/Li + ), which is very close to the theoretical lithium insertion potential of metallic lithium. Therefore, increasing the operating voltage of the lithium ion secondary battery can only improve the intercalation/deintercalation potential of the positive active material.
  • the positive electrode active material significantly enhances the oxidizing ability of the electrolyte, and with the dissolution of transition metal elements (especially manganese), lithium ion secondary batteries cause electrolysis during high temperature storage and cycle testing.
  • the organic solvent of the liquid is continuously oxidized and decomposed, resulting in volume expansion of the lithium ion secondary battery, thereby causing capacity decay and safety hazard of the lithium ion secondary battery.
  • an object of the present invention is to provide an electrolyte and a secondary battery which can simultaneously greatly improve the high temperature cycle performance and high temperature storage performance of the secondary battery.
  • the invention provides an electrolyte comprising: an organic solvent; an electrolyte salt dissolved in an organic solvent; and an additive.
  • the additive includes a silane compound including one or more of the compounds represented by Formula 1; and one or more of dioxane ethers.
  • R 1 , R 2 and R 3 are each independently selected from the group consisting of H, F, Cl, Br, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 2 to 20 alkenyl groups, 2 to 20 alkenyloxy groups, 2 to 20 alkynyl groups, 2 to 20 alkynyloxy groups, and 6 to 26 carbon atoms; One of an aryl group and an aryloxy group having 6 to 26 carbon atoms; and R 4 is selected from the group consisting of an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and a carbon number.
  • R 5 is selected from the group consisting of H, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 1 to 20;
  • An alkoxy group, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, or One of an aryl group having 6 to 26 carbon atoms and an aryloxy group having 6 to 26 carbon atoms; and a hydrogen atom on an alkoxy group, an alkenyloxy group, an alkynyloxy group or an aryloxy group may also be F , one or more substitutions of Cl, Br; alkyl, alkenyl, alkynyl, aryl, alkylene, alkenylene, alkynylene, Hydrogen atom on the group consisting of H, an alkyl group having 1 to 20 carbon atoms, and
  • the invention provides a secondary battery comprising an electrolyte according to an aspect of the invention.
  • the electrolyte of the invention can comprehensively utilize the coordination action of the silane compound and the dioxetane to form a good protective film on the surface of the positive and negative electrodes, thereby reducing the reactivity of the surface of the positive electrode, suppressing the reduction of the electrolyte at the negative electrode and the high potential at the positive electrode.
  • the oxidative decomposition underneath inhibits the elution of the transition metal element and at the same time reduces the impedance growth rate of the secondary battery during the cycle, so that the high-temperature cycle performance and the high-temperature storage performance of the secondary battery can be greatly improved at the same time.
  • the electrolytic solution according to the first aspect of the invention includes: an organic solvent; an electrolyte salt dissolved in an organic solvent; and an additive.
  • the additive includes a silane compound, including one or more of the compounds represented by Formula 1, and one or more of dioxane ethers.
  • R 1 , R 2 and R 3 are each independently selected from the group consisting of H, F, Cl, Br, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 2 to 20 alkenyl groups, 2 to 20 alkenyloxy groups, 2 to 20 alkynyl groups, 2 to 20 alkynyloxy groups, and 6 to 26 carbon atoms; One of an aryl group and an aryloxy group having 6 to 26 carbon atoms; and R 4 is selected from the group consisting of an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, and a carbon number.
  • R 5 is selected from H, an alkyl group having a carbon number of 1 to 20 carbon atoms and 1 to 20
  • An alkoxy group, an alkenyl group having 2 to 20 carbon atoms, an alkenyloxy group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkynyloxy group having 2 to 20 carbon atoms, or One of an aryl group having 6 to 26 carbon atoms and an aryloxy group having 6 to 26 carbon atoms; and a hydrogen atom on an alkoxy group, an alkenyloxy group, an alkynyloxy group or an aryloxy group may also be F , one or more substitutions of Cl, Br; alkyl, alkenyl, alkynyl, aryl, alkylene, alkenylene, alkynylene, The hydrogen atom on the
  • the dioxane ether can preferentially decompose on the positive electrode side during initial charging of the secondary battery and form a uniform and stable protective film on the surface of the positive electrode active material, the protective film It can inhibit the decomposition of the electrolyte (organic solvent or electrolyte salt) at a high potential, and can also inhibit the dissolution of the transition metal at a high potential, thereby effectively improving the high-temperature storage gas production of the secondary battery.
  • the electrolyte organic solvent or electrolyte salt
  • the silylation reaction between the silane compound and the electrolyte on the surface of the negative electrode effectively improves the surface of the negative electrode, and the introduced silicon-oxygen bond is more flexible, which helps to form a more elastic SEI film on the surface of the negative electrode active material, which is better.
  • the simultaneously formed SEI film maintains the film thickness constant during the cycle, and the SEI film is advantageous for improving ion conduction.
  • the fluorosilane formed by the reaction of the silane compound with a trace amount of hydrofluoric acid in the electrolyte can be adsorbed on the surface of the positive electrode to further protect the interface of the positive electrode.
  • the synergistic action of the silane compound and the dioxane ether can be comprehensively utilized to form a good protective film on the surface of the positive and negative electrodes, which can reduce the reactivity of the surface of the positive electrode and inhibit electrolysis.
  • the reduction of the liquid in the negative electrode and the oxidative decomposition at the high potential of the positive electrode inhibits the elution of the transition metal element and reduces the impedance growth rate of the secondary battery during the cycle, thereby simultaneously improving the high-temperature cycle performance and the high temperature of the secondary battery at the same time. Storage performance.
  • the alkyl group having 1 to 20 carbon atoms may be a chain alkyl group or a cycloalkyl group, and hydrogen located on the ring of the cycloalkyl group may be further Alkyl substitution.
  • the lower limit of the number of carbon atoms in the alkyl group is preferably 2, 3, 4, and 5.
  • the preferred upper limits are 3, 4, 5, 6, 8, 10, 12, 14, 16, and 18.
  • an alkyl group having 1 to 10 carbon atoms is selected. More preferably, a chain alkyl group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms is selected.
  • a chain alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 7 carbon atoms is selected.
  • the alkyl group having 1 to 20 carbon atoms may be selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, Isoamyl, neopentyl, cyclopentyl, cyclohexyl, dodecyl, hexadecyl or octadecyl.
  • the alkenyl group having 2 to 20 carbon atoms may be a cyclic alkenyl group or a chain alkenyl group.
  • the number of double bonds in the alkenyl group is preferably one.
  • the lower limit of the number of carbon atoms in the alkenyl group is preferably 3, 4, and 5.
  • the preferred upper limits are 3, 4, 5, 6, 8, 10, 12, 14, 16, and 18.
  • an alkenyl group having 2 to 10 carbon atoms is selected, and more preferably an alkenyl group having 2 to 6 carbon atoms is selected, and more preferably an alkenyl group having 2 to 5 carbon atoms is selected.
  • the alkenyl group having 2 to 20 carbon atoms may be selected from a vinyl group, an allyl group, an isopropenyl group, a pentenyl group, a cyclohexenyl group, a cycloheptenyl group or a cyclooctenyl group.
  • the alkynyl group having 2 to 20 carbon atoms may be a cyclic alkynyl group or a chain alkynyl group.
  • the number of double bonds in the alkynyl group is preferably one.
  • the lower limit of the number of carbon atoms in the alkynyl group is preferably 3, 4, and 5.
  • the preferred upper limits are 3, 4, 5, 6, 8, 10, 12, 14, 16, and 18.
  • an alkynyl group having 2 to 10 carbon atoms is selected, and an alkynyl group having 2 to 6 carbon atoms is more preferably selected, and an alkynyl group having 2 to 5 carbon atoms is more preferably selected.
  • the alkynyl group having 2 to 20 carbon atoms may be selected from an ethynyl group, a propargyl group, an isopropynyl group, a pentynyl group, a cyclohexynyl group, a cycloheptynyl group or a cyclooctynyl group.
  • the aryl group having 6 to 26 carbon atoms may be a phenyl group, a phenylalkyl group, an aryl group having at least one phenyl group (e.g., a biphenyl group), a fused ring.
  • the aromatic hydrocarbon group e.g., naphthyl, anthracenyl, phenanthryl
  • the biphenyl group and the fused ring aromatic hydrocarbon group may be further substituted by an alkyl group or an alkenyl group.
  • an aryl group having 6 to 16 carbon atoms is selected, and more preferably, an aryl group having 6 to 14 carbon atoms is selected, and even more preferably an aryl group having 6 to 9 carbon atoms is selected.
  • the aryl group having 6 to 26 carbon atoms may be selected from a phenyl group, a benzyl group, a biphenyl group, a p-tolyl group, an o-tolyl group, a m-tolyl group, a naphthyl group, an anthracenyl group or a phenanthryl group.
  • an alkoxy group having 1 to 20 carbon atoms can be formed.
  • the alkoxy group having 1 to 10 carbon atoms is selected, and more preferably, an alkoxy group having 1 to 6 carbon atoms is selected, and more preferably, an alkoxy group having 1 to 4 carbon atoms is selected.
  • the alkoxy group having 1 to 20 carbon atoms may be selected from the group consisting of a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, a sec-butoxy group, and a t-butoxy group.
  • an alkenyloxy group having 2 to 20 carbon atoms when the above-mentioned alkenyl group having 2 to 20 carbon atoms contains an oxygen atom, an alkenyloxy group having 2 to 20 carbon atoms can be formed.
  • an alkenyloxy group having 2 to 10 carbon atoms is selected, and more preferably, an alkenyloxy group having 2 to 6 carbon atoms is selected, and even more preferably, an alkenyloxy group having 2 to 5 carbon atoms is selected.
  • the alkenyloxy group having 2 to 20 carbon atoms may be selected from a vinyloxy group, an allyloxy group, an isopropenyloxy group, a pentenyloxy group, a cyclohexenyloxy group, a cycloheptenyloxy group or a cyclooctyl group. Alkenyloxy.
  • an alkyne group having 2 to 20 carbon atoms can be formed.
  • the alkynyloxy group having 2 to 10 carbon atoms is selected, and more preferably, the alkynyloxy group having 2 to 6 carbon atoms is selected, and more preferably, the alkynyloxy group having 2 to 5 carbon atoms is selected. .
  • the alkynyloxy group having 2 to 20 carbon atoms may be selected from the group consisting of an ethynyloxy group, a propargyloxy group, an isopropynyloxy group, a pentynyloxy group, a cyclohexynyloxy group, a cycloheptynyloxy group or a ring.
  • Octenyloxy is selected from the group consisting of an ethynyloxy group, a propargyloxy group, an isopropynyloxy group, a pentynyloxy group, a cyclohexynyloxy group, a cycloheptynyloxy group or a ring.
  • an aryloxy group having 6 to 26 carbon atoms when the aryl group having 6 to 26 carbon atoms as mentioned above contains an oxygen atom, an aryloxy group having 6 to 26 carbon atoms can be formed.
  • an aryloxy group having 6 to 16 carbon atoms is selected, and more preferably, an aryloxy group having 6 to 14 carbon atoms is selected, and still more preferably an aryloxy group having 6 to 10 carbon atoms is selected.
  • the aryloxy group having 6 to 26 carbon atoms may be selected from the group consisting of a phenoxy group, a benzyloxy group, a 4-methylphenoxy group, a 3,5-dimethylphenoxy group, and a 4-methylbenzyloxy group.
  • Base 3-methylbenzyloxy, 2,6-diisopropylbenzyloxy or 1-naphthyloxy.
  • the above-mentioned alkyl group having 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms, and alkyne having 2 to 20 carbon atoms are mentioned.
  • a hydrogen atom on an aryloxy group having 6 to 26 atoms is substituted by a halogen atom F, Cl or Br, a halogenated alkyl group having 1 to 20 carbon atoms and a halogenated group having 2 to 20 carbon atoms are sequentially formed.
  • the halogenated aryloxy group wherein the halogen atom is preferably F or Cl.
  • halogen group to be formed one or more of the halogen atoms F, Cl, and Br are substituted for a part of hydrogen atoms or all hydrogen atoms, and the number of halogen atoms to be substituted is not limited, and preferably It is 1, 2, 3 or 4.
  • a halogenated alkyl group having 1 to 10 carbon atoms, a halogenated alkenyl group having 2 to 10 carbon atoms, and a carbon number of 2 to 10 are selected.
  • a halogenated chain alkyl group having 1 to 6 carbon atoms, a halogenated cycloalkyl group having 3 to 8 carbon atoms, a halogenated alkenyl group having 2 to 6 carbon atoms, and a carbon number are selected.
  • the haloalkynyloxy group having 2 to 6 atoms and the halogenated aryloxy group having 6 to 14 carbon atoms are selected.
  • a halogenated chain alkyl group having 1 to 4 carbon atoms, a halogenated cycloalkyl group having 5 to 7 carbon atoms, a halogenated alkenyl group having 2 to 5 carbon atoms, and a carbon atom are selected.
  • the haloalkynyloxy group having 2 to 5 atoms and the halogenated aryloxy group having 6 to 10 carbon atoms are selected.
  • halogenated group examples include trifluoromethyl (-CF 3 ), 2-fluoroethyl, 3-fluoro-n-propyl, 2-fluoroisopropyl, 4-fluoro-n-butyl, 3-fluorosec-butyl, 5-fluoro-n-pentyl, 4-fluoroisopentyl, 1-fluorovinyl, 3-fluoroallyl, 6- Fluoro-4-hexenyl, o-fluorophenyl, p-fluorophenyl, m-fluorophenyl, 4-fluoromethylphenyl, 2,6-difluoromethylphenyl, 2-fluoro-1-naphthyl , fluoromethoxy, 1-fluoroethoxy, 2-fluoro-n-propoxy, 1-fluoro-isopropoxy, 3-fluoro-n-butoxy, 4-fluoro-n-penty
  • the number of carbon atoms is 1 to 20 alkyl groups, the number of carbon atoms is 2 to 20, the alkynyl group having 2 to 20 carbon atoms, and the number of carbon atoms is 6 to 26 aryl groups
  • the hydrogen atom is substituted by a sulfonic acid group or a sulfonyl group, the corresponding sulfonic acid alkyl group, sulfonic acid alkenyl group, sulfonic acid alkynyl group, sulfonic acid aryl group, alkylsulfonyl group, alkenylsulfonyl group, Alkynylsulfonyl, arylsulfonyl.
  • the sulfonic acid group may be substituted with a part of hydrogen atoms or all hydrogen atoms in the above alkyl group, alkenyl group, alkynyl group or aryl group, and the number of the sulfonic acid groups may be one or two.
  • the sulfonyl group may be substituted with a part of hydrogen atoms or all hydrogen atoms in the above alkyl group, alkenyl group, alkynyl group or aryl group, and the number of the sulfonyl group may be one or two.
  • examples of the sulfonyl group include methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group and n-butyl group.
  • Sulfonyl isobutylsulfonyl, tert-butylsulfonyl, n-pentylsulfonyl, isopentylsulfonyl, neopentylsulfonyl, 2,3-dimethylpropylsulfonyl, 1-ethyl Propylsulfonyl, n-hexylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, cycloheptylsulfonyl, cyclooctylsulfonyl, n-heptylsulfonyl, n-octylsulfonyl, cycloheptylsulfonyl , cyclooctylsulfonyl, propenylsulfonyl, butenylsulfonyl,
  • a sulfonic acid group a sulfonic acid methyl group, a 2-sulfonic acid ethyl group, a 3-sulfonic acid n-propyl group, and the like may be specifically mentioned.
  • the alkyl group having 1 to 20 carbon atoms, the alkenyl group having 2 to 20 carbon atoms, the alkynyl group having 2 to 20 carbon atoms, and the number of carbon atoms When an aryl group of 6 to 26 loses one hydrogen atom, an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, an alkynylene group having 2 to 20 carbon atoms, or the like, An arylene group having 6 to 26 carbon atoms.
  • the alkylene group having 1 to 20 carbon atoms, the alkenylene group having 2 to 20 carbon atoms, the alkynylene group having 2 to 20 carbon atoms When a hydrogen atom on an arylene group having 6 to 26 carbon atoms is substituted by a halogen atom F, Cl or Br, a halogenated alkylene group having 1 to 20 carbon atoms is formed in order, and the number of carbon atoms is 2 to 2
  • one or more of the halogen atoms F, Cl, and Br are partially hydrogen atoms or All of the hydrogen atoms are substituted, and the number of halogen atoms to be substituted is not limited, and preferably one, two, three or four.
  • the silane compound is selected from one or more of the following compounds;
  • the dioxane ether is one selected from the group consisting of 1,3-dioxolane, 1,3-dioxane, and 1,4-dioxane. Or several.
  • the silane compound is one or more selected from the group consisting of Compound 1, Compound 2, Compound 3, Compound 4, Compound 5, Compound 10, Compound 11, and Compound 16. kind.
  • the total mass of the additive may be 0.2% to 10% of the total mass of the electrolytic solution.
  • the mass of the dioxane is from 0.1% to 5% by mass based on the total mass of the electrolyte.
  • the mass of the silane compound is an electrolyte 0.1% to 5% of the total mass.
  • the organic solvent is a non-aqueous organic solvent.
  • the organic solvent may include a cyclic ester and a chain ester.
  • the cyclic ester is selected from one or more of ethylene carbonate, propylene carbonate, butylene carbonate, and tetrahydrofuran.
  • the chain ester is selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, methyl formate, ethyl formate, propyl formate, acetic acid.
  • methyl ester ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, dimethyl sulfite, diethyl sulfite.
  • the mass of the cyclic ester is from 20% to 50% of the total mass of the electrolytic solution.
  • the mass of the chain ester is 40% to 80% of the total mass of the electrolytic solution.
  • the total mass of the organic solvent may be from 60% to 85% of the total mass of the electrolytic solution.
  • the electrolyte salt may be a lithium salt, a sodium salt or a zinc salt, which varies depending on the secondary battery to which the electrolyte is applied.
  • the concentration of the electrolyte salt in the electrolytic solution is from 0.3 M to 1.8 M.
  • the secondary battery according to the second aspect of the present invention may be a lithium ion secondary battery, a sodium ion secondary battery, or a zinc ion secondary battery.
  • the secondary battery according to the second aspect of the invention further includes a positive electrode sheet, a negative electrode sheet, a separator, and a packaging foil.
  • the positive electrode sheet includes a positive electrode current collector and a positive electrode film containing a positive electrode active material provided on the positive electrode current collector.
  • the negative electrode sheet includes a negative electrode current collector and an negative electrode film containing a negative electrode active material disposed on the negative electrode current collector.
  • the separator is spaced between adjacent positive and negative sheets.
  • the packaging foil can be aluminum foil.
  • the positive electrode active material is selected from the group consisting of LiCoO 2 , LiMnO 2 , LiNi 1/3 Co 1/3 Mn 1/3 O 2 , LiNi 0.5 Co 0.2 Mn 0.3 O 2 , One or more of LiNi 0.6 Co 0.2 Mn 0.2 O 2 , LiNi 0.4 Co 0.2 Mn 0.4 O 2 , and LiFePO 4 .
  • the negative active material may be selected from one or more of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, and silicon.
  • the upper limit cutoff voltage of the lithium ion secondary battery is 4.35 V to 4.6 V.
  • the electrolyte salt is a lithium salt.
  • the lithium salt is selected from the group consisting of LiPF 6 , LiBF 4 , LiBOB, LiDFOB, LiAsF 6 , LiClO 4 , LiFAP, LiCF 3 SO 3 , Li(FSO 2 ) 2 N, Li(SO 2 (CF 2 ) 3 SO 2 ) 2
  • N Li(SO 2 R F ) 2 N, Li(SO 2 F)(SO 2 R F )N, R F is C n F 2n+1 , n is an integer of 1-10 .
  • the lithium salt is selected from one or more of LiPF 6 , LiBF 4 , LiBOB, Li(FSO 2 ) 2 N.
  • the upper limit cutoff voltage of the lithium ion secondary battery to which the electrolytic solution of the present invention is applied can reach 4.35 V to 4.6 V.
  • the secondary battery is a sodium ion secondary battery or a zinc ion secondary battery, it is only necessary to change the corresponding positive electrode active material, negative electrode active material, and electrolyte salt.
  • the positive electrode active material LiNi 0.5 Co 0.2 Mn 0.3 O 2 , the conductive agent Super-P, and the binder PVDF are dissolved in a solvent N-methylpyrrolidone at a mass ratio of 97.2:1.3:1.5 to form a positive electrode slurry, and then The positive electrode slurry was uniformly coated on the double-sided current collector aluminum foil, and the coating amount was 0.0102 g/cm 2 , followed by drying at 85 ° C, followed by cold pressing, trimming, cutting, and slitting, followed by vacuum at 85 ° C. After drying for 4 hours under conditions, the tabs were welded to form a positive electrode sheet.
  • the negative electrode active material artificial graphite, conductive agent Super-P, thickener CMC, and binder SBR are mixed in a solvent deionized water at a mass ratio of 95.4:1.2:1.2:2.2 to form a negative electrode slurry, and then the negative electrode slurry is prepared.
  • the material was uniformly coated on the double-sided current collector copper foil, and the coating weight was 0.0071 g/cm 2 , followed by drying at 85 ° C, followed by cold pressing, trimming, cutting, and slitting, followed by vacuum at 110 ° C. After drying for 4 h, the tabs were welded to prepare a negative electrode sheet.
  • the electrolyte solution has a lithium salt of 1 mol/L of LiPF 6 and an organic solvent of a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC), wherein the mass ratio of EC and EMC is 30:70. Further, the electrolyte further contains an additive which is a 1,3-dioxolane which accounts for 1% of the total mass of the electrolyte and a compound 5 which accounts for 2% of the total mass of the electrolyte.
  • EC ethylene carbonate
  • EMC ethyl methyl carbonate
  • the positive electrode sheet, the negative electrode sheet, and the separator are subjected to a winding process to form a battery core having a thickness of 5.7 mm, a width of 16 mm, and a length of 33 mm, wherein the battery core has a long air bag. In order to observe its gas production.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and 2% of the total mass of the electrolyte. The total mass of the liquid is 2% of compound 5.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte. The total mass of the liquid is 2% of compound 5.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolyte (ie, step (3)), the additive was 1,3-dioxolane and 4% of the total mass of the electrolyte.
  • the total mass of the liquid is 2% of compound 5.
  • a lithium ion secondary battery is prepared according to the method of Example 1, except that in the preparation of the electrolyte (ie, step (3)), the additive is 1,3-dioxolane and occupies 5% of the total mass of the electrolyte. Liquid Compound 5 with a total mass of 2%.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte.
  • the total mass of the liquid is 1% of compound 5.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte. The total mass of the liquid was 3% of Compound 5.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte. The total mass of the liquid is 4% of compound 5.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte. The total mass of the liquid is 5% of compound 5.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte.
  • the total mass of the liquid was 2% of Compound 1.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte. Liquid Compound 2 with a total mass of 2%.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte.
  • the total mass of the liquid is 2% of compound 3.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxolane and occupies 3% of the total mass of the electrolyte. The total mass of the liquid is 2% of compound 4.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,4-dioxane and 3% of the total mass of the electrolyte.
  • the total mass of the liquid is 2% of compound 13.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxane and 3% of the total mass of the electrolyte.
  • the total mass of the liquid is 2% of compound 14.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,4-dioxane and 3% of the total mass of the electrolyte. The total mass of the liquid is 2% of compound 5.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolytic solution (ie, step (3)), the additive was 1,3-dioxane and 3% of the total mass of the electrolyte. Liquid Compound 5 with a total mass of 2%.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that in the preparation of the electrolytic solution (i.e., the step (3)), no additive was added.
  • a lithium ion secondary battery is prepared according to the method of Example 1, except that in the preparation of the electrolyte (ie, step (3)), the additive is 0.05% of the total mass of the electrolyte, 1,3-dioxolane and electrolysis Compound 5 was 0.05% of the total mass of the liquid.
  • a lithium ion secondary battery was prepared according to the method of Example 1, except that in the preparation of the electrolyte (ie, step (3)), the additive was 1,3-dioxolane and occupies 6% of the total mass of the electrolyte.
  • the total mass of the liquid was 6% of Compound 5.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that in the preparation of the electrolytic solution (i.e., in the step (3)), the additive was 1,3-dioxolane in an amount of 3% by mass based on the total mass of the electrolytic solution.
  • a lithium ion secondary battery was prepared in accordance with the method of Example 1, except that in the preparation of the electrolytic solution (i.e., the step (3)), the additive was Compound 5 which was 2% by mass of the total mass of the electrolytic solution.
  • the lithium ion secondary battery was first charged to 4.5 V with a constant current of 0.5 C, further charged to a current of 0.025 C at a constant voltage of 4.5 V, and then discharged to a lithium ion secondary battery at a constant current of 0.5 C. To 2.8V, this is a charge and discharge cycle, and the discharge capacity of this time is the discharge capacity of the first cycle.
  • the lithium ion secondary battery is subjected to a cyclic charge and discharge test in the above manner, and the first Discharge capacity of 100 cycles.
  • Capacity retention ratio (%) after 100 cycles of the lithium ion secondary battery [discharge capacity at the 100th cycle / discharge capacity at the first cycle] ⁇ 100%.
  • the lithium ion secondary battery was first charged to 4.5 V at a constant current of 0.5 C at 25 ° C, further charged to a current of 0.025 C at a constant voltage of 4.5 V, and then the lithium ion secondary battery was drained in deionized water.
  • the initial volume (the volume before the high-temperature storage of the lithium ion secondary battery) was measured and stored at 60 ° C for 30 days. After the storage was completed, the volume of the lithium ion secondary battery after high-temperature storage was tested.
  • volume expansion ratio (%) of lithium ion secondary battery after high temperature storage [(volume after high temperature storage of lithium ion secondary battery - volume before high temperature storage of lithium ion secondary battery) / before high temperature storage of lithium ion secondary battery Volume] ⁇ 100%.
  • the lithium ion secondary battery to which the dioxane ether and the silane compound of the present invention are added has better high-temperature cycle performance and high-temperature storage than the lithium ion secondary battery of Comparative Example 1 without adding any additive. performance.
  • Comparative Example 4 the addition of dioxane ether alone can only form a good interfacial film on the positive electrode side unilaterally, inhibiting the oxidative decomposition of the electrolyte on the positive electrode side, and the organic solvent can be continuously reduced and decomposed on the negative electrode side.
  • the generation of gas also causes a decline in the capacity of the lithium ion secondary battery.
  • the high-temperature storage performance of the lithium ion secondary battery is still relatively improved, because the interface film formed on the surface of the positive and negative electrodes by the high content of the dioxetane and the silane compound lowers the reactivity of the surface of the positive electrode, thereby The reduction of the electrolyte at the negative electrode and the oxidation of the positive electrode are effectively suppressed.
  • the content of the dioxetane and the silane compound is less than 0.1% (Comparative Example 2), the improvement in the high-temperature cycle performance and the high-temperature storage property of the lithium ion secondary battery is not remarkable.
  • Example 3 It can be seen from the comparison of Example 3 and Examples 10-15 that the larger the molecular weight of the substituent, the larger the spatial structure of the compound, and the more improved the high-temperature cycle performance and high-temperature storage performance of the lithium ion secondary battery. it is good. This may be due to the fact that in the silane compound, a larger substituent forms a larger steric hindrance on the surface of the negative electrode, which better prevents further contact reduction of the electrolyte at the negative electrode. Further, since the compound 4 and the compound 5 contain an unsaturated olefin, the negative electrode is more easily reduced, which is more advantageous for the stability of the SEI film.

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Abstract

L'invention concerne une solution électrolytique et une batterie rechargeable. La solution électrolytique comprend : un solvant organique ; un sel d'électrolyte dissous dans le solvant organique ; et un additif. L'additif comprend : un composé de silane, comprenant un ou plusieurs des composés représentés par la formule 1 ; et un ou plusieurs des éthers dioxo-cycliques. La solution électrolytique peut utiliser de manière exhaustive un effet synergique du composé de silane et de l'éther dioxo-cyclique pour former un bon film protecteur sur les surfaces d'une électrode positive et d'une électrode négative, capable de réduire l'activité de réaction de la surface de l'électrode positive, de supprimer la réduction de la solution électrolytique sur l'électrode négative et la décomposition oxydative de celle-ci à un potentiel élevé de l'électrode positive, et de supprimer l'élution d'un élément de métal de transition. En même temps, le taux de croissance d'impédance de la batterie rechargeable pendant le cycle peut être réduit. Par conséquent, les performances du cycle à haute température et les performances de stockage à haute température de la batterie rechargeable peuvent être grandement améliorées simultanément.
PCT/CN2017/093376 2016-08-12 2017-07-18 Solution électrolytique et batterie rechargeable Ceased WO2018028392A1 (fr)

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CN110176622B (zh) * 2019-05-15 2022-05-24 华南理工大学 一种金属锂二次电池电解液及其制备方法与应用
CN114284556A (zh) * 2020-09-18 2022-04-05 浙江蓝天环保高科技股份有限公司 一种锂离子电池电解液及锂离子快充电池
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CN117080564A (zh) * 2023-09-28 2023-11-17 宁德时代新能源科技股份有限公司 电解液、电池单体、电池和用电装置

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